Cobalt complexes of monoazo dyes



. 8 2 COBALT COMPLEXES 0F MONOAZO DYES Robert Frederic MichelSureau, l lnghien-les-Bains, and- Georges Raymond Henry Mmgassou, Paris, France, assignors to Compagnie Francaise des Matieres Colorantes, Paris, France, a French company No Drawing. Application July 25, 1955 Serial No. 524,288

Claims priority, application France July 26, 1954 6 Claims. (Cl. 260-146) The'present invention relates to dyestuffs of the general formula:

in which R represents the residue of a diazotizable base having, in the ortho position to the NH group, a group capable of taking part in the formation of a metalliferous complex, but containing neither an SO H group nor a COOH group other than the COOH group which may eventually be present in the ortho position 'to 'the NH Q group, and R represents a heterocyclic nucleus, esp'epound thus obtained with a coupling agent of the general f formula:

, CH;-CO- CH:-CON HR' V (II) R and R having the same significance as above. The

dyes may then be converted into metalliferous complexes;

ICC

lead to metalliferous complexes containing less than one atom of the complexing metal per molecule of mono-azo dye. All the methods leading tocomplexes which correspond to this last constitution can be used, and among these must be included those employing chroming in presence of amides or of ammonium salts of carboxylic acids, of aromatic ortho-hydroxycarbocylic acids, of aliphatic hydroxycarbocylic acids, ofaminocarbocylic acids, heating in the alkali metal salts of aliphatic monocarboxylic acids containing water of crystallisation in the presence of a metallising agent, chroming in the presence of organic solvents, heating in aqueous solution in presence of a salt of cobalt, nickel, copper, iron, manganese or. aluminium and of an excess of caustic soda, if desired in the presence of an aliphatic hydroxycarbocylic acid, the'reaction of the non-metallised dyestufif with a metallising agent inthe presence of another metallisable dyestuff, or the reaction of the .non-metallised dyestuif with Among the groups capable of taking part in the formation of a metalliferous complex, and which must be foundin the ortho position to the NH; group of the diazotizable bases utilisable as starting materials for the preparation of the *dyestuifs which are the object of the invention, there may be mentioned the --OH, OCHg,

OCH; COOH,and COOH groups. The diazotizable bases may also contain other substituents such as halogen atoms and the alkyl, OCH NO acylamino, arylamino, SO NH alkylsulphonylamino, arylsulphonylamino, CO-alkyl, and sulphone (SO CH SO C H for example) groups.

The coupling agents used are those of the general groups which do not confer solubility, and of the acylacetyl derivatives of aminocarbazoles.

The conversion of the mono-azo dyestufi thtisQprea metalliferou s dyestuff containing one molecule of metal per molecule of dyestufi.

, Thermetalliferous dyestuffs obtained according to the present invention may be employed for the coloration of organic solvents, lacquers, varnishes and materials based on cellulosic esters and ethers. Some of these dyestuffs, especially those] containing g and -SO NH SO2NHCH3, SO2CH3, or -SO2C2H5 group in the residue R of the general Formula I, are capable of dyeing, in a neutral or weak acetic acid bath, wool, natural silk, leather, animalised fibres, superpolyamides and superpolyurethanes, giving shades which show excellent general fastness, while thevegetable and acetate rayon fibres areleftuncoloured.

The invention will be more clearly understood by reference to the following examples, in which the parts indicated areparts by weight, and which are purely illustrative.

' Example 1 2.3 parts of 2-acetoacetylarnino-benzthiazole are dissolved in 30 parts'of Water'andZ parts of 36 B. soda lye. Into this is gradually run a'solution of the diazo compound obtained by diazotizing a solution of 2.3 parts of 2-a mino-4-sulphonamido-l-hydroxy-benzene in parts of water and 2.5 parts of 22 B. hydrochloric acid by the addition of 5 parts by volume of a solution of 2 N sodium nitrite between 0. C. and +5: C. The alkalinity of them'edium'is'maintained by the addition of a '65 Formula H. They may consist, for example, of the solution of sodium carbonate. The mixture is agitated for a further hour at 3040 C., then the yellow dyestufi which is precipitated is filtered, washed with a little cold water and dried at C. 7

7 3 Example 2 A solution of one part crate" dyestiifi from the previous example in 50 parts of water to which soda lye has been added sothat the pH may be in the region of 10, is

brought to boiling under reflux. 17.5 parts by volume pared into metalliferous dyes may take place according to any generally known method of metallization; in particular, it can be efiected by metallising treatments which of a solution of sodium cobaltotartrate containing 14.75 grammessfof cobalt per litre are added. The dyestuff rapidly becomes soluble. When a drop on filter paper no longer changes eo'leur with acetic'a'cidfthe mixture is allowed to cool and the dyestuif is precipitated by sodium chloride, andis filtered and dried. This dyestutf dyes 'wool from anammonium acetate bath in a yellow shade,

which is'very to light and possessed of good fastness to humidity tests.

methylthio-benzthiazole.

reflux. 7.5 parts by volume of a solution of sodium chromotartrate, containing 10.4 g. of chromium per litre, are added. After 5 hours, the mixture is left to cool and is precipitated by sodium chloride and a little sodium bicarbonate, filtered and the precipitate dried. From a neutral bath, the dyestuflf dyes wool an orange-yellow.

Other examples are summarised in the following table:

Example Base dlazotlzed Coupling component chromium cobalt 4.; 20min o-4-sulglgonam ido- N pale yellow golden yellow.

l-hydroxynzeue.

OONH- O-GHa 5 -Qdo OO-OH; reddish yellow pale yellow.

Hi N O-NH 0-OOIH5 .Q

a do N golden yellow golden yellow.

H|C v V C-BC3H| CO-NH H: v s I 7 do-.. N .do Do.

o-s-om CO-NH Hg 1 S t 0- 011, s 'rln C0--GH reddish yellow brlght golden yellow N ii 7 O-NH CH. S

n 'dn N yellow orengezoldenyellow.

- CH a cs-om oo-NH V HI 10 do i N pale yellow reddish yellow.

"011.0 A CS-CH;

co-mr O-GH| 11 .do N yellowish orange bright golden'yellow.

GS-OH; co-NH' 12 ..do .Q N\ yellow orange....... golden yellow.

f o-s-olm oo-Nn I .L 8

Colour on wool 01' the complex from p 7,. r H r v, I Oolouronwoolol'theoomplextrom- Example Base dlazottzed Coupllng component W v V H I u chromium cobalt 23 .rd0... i H reddish yellow g yellow.

41 N O-NH \CQHI OHIO 24-. do yellorvlsh orange. bright golden yellow.

r-C Q.v GIHJO S HI OKs-$0 r. 25 do N\ pale yellow golden yellow.

\MH' J 25 do orange yellow "I Do.

27 4-nltr0-24mtno-phenoL- orange yellow.

28 4-ohloro-2-amJno-5- N yellow orange.. Do. mlphon-amido-phenol. p 7 CNH-GO I H:

We claim: ethyl, methoxy and-tethoxy groups which complexes conl. The cobalt complexes of a mono-azo dyestutf :se- Q lected from those having the following formulae:

in which X represents a member selected from the group consisting of the OH and --COOH groups, the henzene nucleus A is substituted by members selected from i the group consisting of hydrogen and chlorine atoms and the methyl, nitro, acylamino, sulphonamido, monomethylsulphonylamino, dimethylsulphonylamino, isopropylsulphonylamino, methylsulphone and ethylsulphone groups,

ing of the hydrogen and chlorine atoms, and th methyl,

lainone atom of cobalt per two molecules of dyestufi.

2. The cobalt complexes of a mono-azo dyestufi selected from those having the following formulae:

in which the benzene nucleus A is substituted by members selectedtrom the group consisting of hydrogen and chlorine atoms and the nitro and sulphonamido groups,

Y represents a member selected from the group consisting of the hydrogen atom and the methyl, ethyl, phenyl,

methoxy, ethoxy, methylthio and ethylthio groups and Z represents a., m ember'selected from the group consisting of the hydrogen and.;ghlorine atoms and the methyl, ethyl, methoxy andvethoxy groups which complexes cona n one atom of cobalt per two molecules of dyestuff.

3. The cobalt complex of the mono-azo dyestufi of the formula:

which complex contains one atom of cobalt per 2 molecules of dyestutf.

5. The cobalt complex of the mono-azo dyestutf of the formula:

10 which complex contains one atom of cobalt per 2 molecules of dyestutf.

6. The cobalt complex of the mono-azo dyestufi of the formula:

which complex contains one atom of cobalt per 2 molecules of dyestutf.

References Cited in the file of this patent UNITED STATES PATENTS 2,030,327 Schrader et a1. Feb. 11, 1936 2,195,011 Petitcolas et a1 Mar. 26, 1940 2,499,133 Conrad Feb. 28, 1950 2,500,093 Petitcolas et a1 Mar. 7, 1950 OTHER REFERENCES Venkataraman: Synthetic Dyes, vol. 1, 1952, pps. 540- 41. 

1. THE COBALT COMPLEXES OF A MON-AZO DYESTUFF SELECTED FROM THOSE HAVING THE FOLLOWING FORMULAE: 